Search Documents

By Ursula E. Wolff

The precipitation of carbides from an alloy containing 33 pct Ni, 21 pct Cr, balance iron, was investigated electron microscopically by means of extraction replicas and thinned metal foils. Annealing temperatures ranged from 565°to 870°C and up to several thousand hours. M23C6 precipitated in pain boundaries, incoherent and coherent twin boundaries in that sequence. The orientation relationship between carbides and austenite matrix was determined and correlated with the morphology of the carbides and with the type of boundary in which precipitation occurred. In large-angle grain boundaries, as well as in coherent twin boundaries, the carbides had the same orientation as one of the adjacent pains. These carbides formed sheets of individual flakes with shapes related to the orientation of the boundary. In incoherent twin boundaries carbides precipitated in ribbons composed of pavallel rods. An unidentified subcarbide was found to precede precipitation of M23C6 in these boundaries. The M 23 C6 rods had a kind of fiber texture with (110) parallel to the long dimension of the rods and ribbon, and with orientations of both of the adjacent twin-related austenite crystals Predominant in the texture of the carbide. A hard sphere crystal model has been used to discuss orientation and morphology of the carbides in terms of free volume and vacancies available in the boundaries. A number of papers have dealt with the morphology of chromium carbide (M23 C6) precipitated in austenitic stainless steels.1"7 In all these investigations, the carbides were examined in the electron microscope by means of extraction replicas. With this technique, the carbides retain the spatial distribution they had in the bulk sample. However, since the matrix is dissolved in the process, the particles can turn in an unpredictable way; and the orientation relationship between matrix and carbides cannot be established. In this paper the results of studies on extraction replicas and on thinned metal foils are reported. These studies were undertaken to determine the matrix-to-car bide orientation relationship, and to correlate the orientation of the carbides with their morphology. PROCEDURE The material used was an austenitic alloy with 33 pct Ni, 21 pct Cr, balance iron, containing approximately 0.05 pct C. Coupons of 1.25-mm sheet were first solution-annealed at 1050°C for 15 min and air-cooled. Then, to precipitate the carbides, samples were isothermally annealed in the range from 565" to 870°C for times up to several thousand hours. All further specimen-preparation procedures were carried out after the final anneal. Carbon extraction replicas from polished and etched surfaces were made with 10 pct bromine in methyl alcohol.' Thin foils were prepared from punched-out 3-mm-diam disksg which fit into the electron-microscope holder. The disks were prethinned by grinding to approximately 0.5 mm thickness, and then electro-polished in a polytetrafluoroethylene holder1' with a solution containing 5 pct perchloric acid in acetic acid to which 10 g per 1 Cro3 and 5 g per 1 nickel chloride were added (etchant modified from that of Briers et al."). This solution dissolves neither the carbides nor the austenite around the carbides preferentially. By using extraction replicas, electron micrographs and selected-area electron-diffraction patterns were taken from the same carbide arrays. By using thin foils, electron micrographs were made from a grain boundary area containing carbides. Electron-diffraction patterns were then taken from the same area and from each of the adjacent grains separately. In this manner, the orientation of each grain could be determined without interference by the carbide pattern. A peculiarity of extraction replicas should be pointed out. After the matrix is etched away, the carbide arrays float freely in the etching and washing solutions, and are held in place only at the anchoring points in the carbon replica. When the replica is picked up with a screen the carbide arrays tend to flip to one side. Thus, while the surface features are preserved, the original arrangement of the carbides may severely and unpredictably be disturbed whenever the specimen contains large amounts of interconnected carbides. Nevertheless, it is possible to correlate the different morphologies of the carbides with the type of boundary in which they have precipitated. RESULTS 1) Extraction Replicas. Fig. 1 shows that the grain boundaries usually are curved, multicornered surfaces of random orientation. The coherent twin boundaries (which are (111) planes) cut a grain into parallel slices. Incoherent twin boundaries occur at the ends and on the steps of twins and are often narrow, parallel-sided strips which are much longer than they are wide. Different morphologies can clearly be distinguished for the M23Ce carbides precipitated in each of these types of boundaries, and agree well with those observed by kinzel.2 The kinetics of this precipitation has been investigated." The first carbides precipitate in junctions of three grain boundaries and fan out from there into the adjoining boundary surfaces, Fig. 2(a). These carbides are oriented randomly, Fig. 2(b), and become coarser and thicker as annealing time increases. The large-angle grain boundaries are next to fill

Jan 1, 1967

By J. H. Scaff, W. G. Pfann

The effects of impurities on the electrical properties of silicon are discussed in a companion paper by Messrs. Scaff, Theuerer, and Schumacher.' It was shown that an ingot of silicon which contained boron and phosphorus in certain concentrations consisted partly of p-silicon and partly of n-silicon2 and that the common boundary between these regions was the source of a photo-voltage. These features were ascribed to the segregation of boron and phosphorus during solidification of the ingot. Because of different rates of segregation the first portion of the ingot to freeze contained a molar excess of boron over phosphorus and hence was p-silicon. The last-solidified region contained a molar excess of phosphorus and was n-silicon. This paper is concerned with the microscopic examination of such ingots. The microstructures are rather unusual in certain respects and their study has helped to show how the segregation of minor elements modifies the electrical properties of silicon. The microstructures of ingots prepared from two lots of silicon, designated 1 and 2, will be described. These lots were obtained from the Electro Metallurgical Co. Both contain 99.8+ pct silicon, but they differ in impurity analysis. For each lot will be shown the microstruc-ture of a slowly cooled ingot, for which the time of solidification is 6 min., and that of a rapidly cooled ingot, for which the time of solidification is 2 min. The ingots were prepared from 45 g charges of silicon. When an alloy freezes a cored structure is generally produced because of insufficient diffusion to remove concentration differences established during freezing. As a result of coring the first portion of a crystal to freeze is usually poorer in solute than equilibrium requires, while the last material to solidify is richer. In a columnar grain, growth is principally unidirectional and coring can produce a concentration gradient along the entire grain. By carrying the picture of the coring process from a single grain to an entire ingot in which columnar grains are aligned more or less radially, one can easily see that a composition gradient could be established between the outside and center of the ingot. This, to a considerable extent, occurs during the solidification of a slowly cooled ingot of silicon. Slowly Cooled Ingot In slowly cooled ingots of both lots of silicon, columnar grains which are approximately radial in direction and longest at the top of the ingot enclose a region in which the shapes and align- ment of the grains are considerably less regular. The central region is last to solidify and contains cavities and inclusions. The sketch of Fig 1 illustrates some of these features, as well as others which will be described below. If a polished section of an ingot is etched in a mixture of 2 parts of 20 pct HF and 98 parts of HNO3 the p-n barrier becomes visible. The overall shape of the barrier in a slowly-cooled ingot is roughly oval, as may be seen in Fig 1. The proportion of n-silicon, that is, the region enclosed by the barrier, is considerably greater in ingots of lot 1 than in those of lot 2. A sample about 34 x 1/8 X 1/8 in. was cut from a slowly cooled ingot of lot 1 with its long direction extending from the top of the ingot to the porous region. Thus its upper half was psilicon, its lower half n-silicon. A longitudinal face was polished and etched in the acid mixture. The areas of interest are identified in Fig 2. A band of parallel markings extends across the sample in the columnar region. These striae are roughly parallel to the upper surface of the ingot and cross grain boundaries with only slight deviations. They are quite distinct in the n-silicon,

Jan 1, 1950

By Lyman Johnson

Single crystals qf copper in "single slip" orientatiorzs have been deformed in compression. During defortnation all of the independent deformation parameters have been measured. These parameters consist of thefive strain components and three components descrihing the lattice rotation. By a finite strain analysis these pararmeters , forrming a deformation gradient martrix, are related to the amounts of slip on each of the twelve slip systems. The results show that the amount of secondary slip is about equal to the amount of primary slip. This is an order of magnitude larger than has been believed previoutsly. ACCORDING to early theory and experiments, when a single crystal of a fcc metal is deformed in tension or compression it should deform by slip on only one slip system until the stress axis reaches a symmetrical orientation.' However. the observation of a large increase in the secondary dislocation density during ..single slip" makes it clear that some slip does occur on secondary systems. Knowledge of the amount and distribution of this secondary slip is essential to a complete understanding of the mechanisms of single-crystal deformation. Ahlers and Haasen 2 and Mitchell and Thornton1 have tried to detect the amount of secondary slip in single crystals of silver and copper, respectively. Each simultaneously measured the angle A, between the tensile axis and the primary slip direction and the length 1 of a gage section of the specimen after incremental amounts of deformation in tension. The measured A, was then compared with the theoretical single slip angle hp. given by sin Ap = j sin . hO where ?o was the initial angle between the tensile axis and the primary slip direction and lo was the initial gage length. In both sets of experiments a small but systematic difference between ?e and ?p was found. This difference must be due to the occurrence of secondary slip. However, as Mitchell and Thornton1 pointed out. nothing quantitative can be said about the amount and distribution of this secondary slip from the measurements that they made. The reason that no quantitative conclusions could be made is because no unique solution for the distribution of slip on the twelve fcc slip systems can be determined from only two measured deformation parameters such as A and 1. There are, in fact, eight independent macroscopic deformation parameters that can be measured when a single crystal undergoes a homogeneous deformation. Physically these can be thought of as the five finite strain components and the three angles describing the crystal lattice rotation. All eight of these parameters were measured by Taylor4,5 for aluminum deformed in tension and compression. At that time the concern was to show that slip occurs on {111 (110) systems in fcc metals, and the mathematics were not available to determine what slip distributions were compatible with the measurements. In this paper the mathematics6,7 are developed that allow the slip distribution to be determined from these measurable macroscopic deformation parameters. The analysis is applied to the measurements of the strain and lattice rotation of copper single crystals deformed in compression. The results show that the amount of secondary slip is an order of magnitude larger than had previously been thought. CRYSTALLOGRAPHIC DESCRIPTION OF A HOMOGENEOUS DEFORMATION The deformation of a solid body can be represented by a transformation matrix F that transforms the un-deformed state into the deformed state. Consider a vector X connecting two material points in the unde-formed material and the vector x connecting the same two material points after deformation, where both vectors are referred to the same set of Cartesian axes. The final vector x is related to the initial vector X by the equation: X = FS. [2] Eq. [2] can be considered as the equation defining F, which is called the deformation gradient matrix. Its components are: If the deformation is homogeneous, the transformation is linear and the components of F are constants. Using subscript notation, if P is the unit vector in the initial direction of a material line, the components of the unit vector p in the direction of the same material line after deformation are given by:

Jan 1, 1970

The Hadsel Mill. By R. G HALL (Trans, vol 112 4000 words) This mill is designed to effect the entire reduction of ores by combined crushing and grinding from mine run size to material sufficiently fine for the usual operation of flotation or cyaniding The work is begun and completed in the same machine. The machine is designed on the principal of the elevator wheel, and crushing and grinding are accomplished by dropping a mixture of ore and water upon specially placed "breaker plates" in such a manner that the resultant material passes back into the buckets of the wheel for further elevation One method of removal of the finished product is to permit an overflow of wet pulp on one side of the mill through coarse screens A recent improvement provides for the removal of a pulp by a launder part way up the path of the buckets In either case the pulp passes to a classifier, and the oversize back to the mill in the manner familiar in ball-mill practice Although hardly through the development stage, the machine has given a very good account of itself in simplification of plant, by elimination of coarse and fine crushers with consequent reduction of installation cost and power consumption As compared with the ball mill alone, there is a reduction of power consumption as well as a material reduction of grinding steel There is an increase in cost of maintenance other than grinding steel, but as the machine passes out of the development stage there is a show¬ing of reduction of costs on this item It seems probable that with further develop¬ment and strengthening of the weaker parts further improvement may be made Ball Milling. By A. M Gow, M GUGGENHEIM, A. B. CAMPBELL AND W. H COGHILL. (Tech Pub 517; also Trans, vol 112. 24,000 words) This paper outlines a new philosophy in ball milling by using power as an index of mill operation and ascertaining the effects of the set and induced variables By recognizing the amount of ore in the mill as an important induced variable and recognizing that the amount of ore in the mill depends principally on the size of the discharge trunnion, ball volume, rate of feed, and speed of mill, obstacles formerly met were surmounted When the amount of ore in the mill is dealt with intelligently and the applied work is proportional to the amount of feed, series testing, which would otherwise give a hotchpotch, gives concordant results The study of ball paths and trajectories was seen to be fruitless when it was shown that the old attrition theory for slow mill speed

Jan 1, 1935

By T. O. Anderson, E. J. Stahl

Tests to increase knowledge concerning the process of hydraulic fracturing have been performed on three wells in the Allegheny field in western New York. The fracture orientation and its physical appearance at the well-bore was determined by impression packers run at appropriate times throughout the program. Fract~tre azi171uth and its dimensions thus determined were compared to the rock properties and treatment conditions. Logs to provide data concerning rock properties and to improve identification of vertical fractures were run before each step of the fracture treatment. Pressure osc~illu~iot~s were studied after each phase of tile treatments surface pressures during treatment. These measurements show that subsurface pressures exhibit many of the same characteristics as surface pressures during treatment of a well; however, transient pressures are dampened and deelayed in time at the bottom of the well when COmpared with surface pressures. Data obtained from this study provides a means to help locale and determine orientation of vertical fractures made in the open wellbore. Although these rests were performed in only one area, much of the information gained may be applied to fracturing programs in orher areas. INTRODUCTION In this study, various tests were made to provide data to better understand formation fracturing in situ. The reservoir studied is the Richburg oil sand which is a part of a series of predominantly grey sandstones and shales with occasional brown sandstone layers, known as the Caneadea unit of the Canadaway group of Upper Devonian age. Average physical characteristics of 12 cored wells in this area are 13-ft thick gross sand formation, 12-ft thick net sand. 1.7 md permeability, 11 percent porosity, 44 percent oil saturation (before secondary recovery) and 16 percent water saturation (before secondary recovery). This particular area of the Allegheny oil field was originally drilled prior to 1890. The first waterflood secondary recovery attempt was made in 1929. The present sustained waterflood development began in 1951 and is being carried out on a 4.5 to 5-acre spacing. Objectives of these tests were to (I) study fracture azimuth and dimension in relation to rock properties and treating conditions, (2) improve fracture identification techniques, (3) compare surface and subsurface pressure during all phases of treatment and (4) compare the periods of the fluid column oscillations occurring after each phase of treatment. Although the areas of investigation listed appear divergent in purpose, the program was designed primarily to increase knowledge of down-hole conditions leading to rock failure and extension of the fracture thus created. TEST PROCEDURES Wells upon which tests were conducted are designated as Wells 1 through 3. Well 2 was located 440 ft north of Well 1, and Well 3 was located approximately 880 ft west of Well 1. Wells 1 and 2 were completed with cable tools, while the producing interval of Well 3 was rotary cored using fresh water as the drilling fluid to obtain oriented cores. Tests were divided into separate phases on each well as the fracturing program progressed and consisted of measurements performed prior to treatment, during and after the formation breakdown operation. during fracture treatment and after treatment. To verify location and azimuth of the fracture created, and to obtain an impression of wellbore irregularities, a packer was used (Fig. 1). This packer was lowered on tubing into the wellbore opposite the interval under study and inflated in stages to allow the impression material to conform to the wall of the wellbore. A magnetic compass was attached to the tool for orientation reference. Impressions made prior to treatment showed no existing fractures in the wells under study. Impressions made after both formation breakdown and treatment pro-

COMPARED with the equipment used in most industrial processes, the open-hearth furnace has a relatively short life. The most important quality of an open-hearth refractory, therefore, is its rate of failure. This discussion of the physics and chemistry of the individual refractory materials will keep uppermost the question "Why, how, and where does it fail?" CAUSES OF FAILURE The principal causes of failure of open-hearth refractories are, in their order of importance : 1. Reaction with iron oxides. 2. Reaction with slag. 3. Flow and failure under load. 4. Melting. 5. Spalling. 6. Mechanical breakage. Reaction with Iron Oxides and Slag. Reaction with iron oxides and slag is by far the most important cause of failure. Liquid iron oxide comes near to being the "universal solvent" sought for by the alchemists. Among the materials commonly used in the open-hearth furnace, magnesia has the greatest resistance to this liquid and fireclay the least. The relations of iron and oxygen at high temperatures are illustrated in Fig 14-18. The liquid iron oxide that forms wherever iron is in contact with air or combustion gases cannot be given a definite formula. The percentage of oxygen at steelmaking temperatures may range from 21 to 28 (iron 79 to 72), depending upon the temperature and the oxygen pressure and also upon whether or not the liquid is in equilibrium with metallic iron. Oxide mixtures exist not only in the solid and liquid phases but also in the vapor phase, for metallic iron and its oxides have

Jan 1, 1964

By Everett M. White

Numerous articles have been written in regard to the man who mines coal and he has been likened to brave men in all ages who have gone out to conquer some unknown hazard. Now, however, modern mining is no longer something to be avoided but is a vocation that anyone can well be proud of, with remuneration equal to or above that of almost any industry. A concerted effort is being made each day by both the operator of most mines as well as the state and Federal inspectors to see that coal mines are as safe or safer than any other industry. However, it is true that mine fires and explosions have occurred in the mining industry since its earliest inception. One of the earliest accurate references to such an occurrence is found in the transactions of the Royal Society of London. In the Colliery Managers' Handbook, 1898, Caleb Pamely writes of an explosion that occurred at Fatfield, England, which resulted in the death of 69 persons in August 1708. It is interesting to note that he states, "Three of them, viz, two men and a woman, were blown quite up from the bottom of the shaft, fifty-seven fathoms deep, into the air, to a considerable distance from the mouth of the pit." From this statement it is noted that women were employed as miners in England during that period. Numerous mine fires and explosions have occurred in mines in this and other countries. Several of them claimed more than 100 lives. Among the greatest losses was a mine explosion in West Virginia that claimed 361 and a mine fire in Illinois that claimed 259. Although no one would minimize the seriousness of a mine fire or an explosion, yet in too many cases they have been publicized out of proportion. This especially is so when compared with the accident rate of other industries or on our highways. It should be remembered that of these general classifications of hazards in mining, mine fires and explosions rank very low in the accident rate in any given year. In modern times the coal industry has completed two years or more, at various times, without a single major disaster. The

Jan 1, 1973

By Eugene H. Dawson

MICA is a mineral that once was a familiar sight as fireproof windows in stove and furnace doors and as lamp chimneys and shades. Since 1878, the beginning of the electrical age, the use of mica for such purposes has gradually declined and its use in electrical equipment and appliances has developed to such an extent that the known sources of supply are scarcely equal to the demand. With the increasing capacity of electric generating units, the size of mica sheets found in nature was inadequate. However, in 1894, a process was developed whereby thin films or splittings cemented with shellac or other binders could be pressed into large sheets. 18 The introduction of radio in the early 1920s created such a heavy demand for the smaller sizes of mica that on March 22, 1938, mica was included among 23 commodities on the list of strategic materials approved by the United States Army and Navy Munitions Board. To be included in this list, the material must be one whereof the domestic supply is not sufficient to meet the demand. COMPOSITION Mica is a complex mineral composed principally of the silicates of potassium, aluminum, and magnesium. Less prevalent species contain, as essential components, lithium, vanadium, and chromium. Iron usually is present either as an essential component or as an impurity. The mica group comprises some nine different species, five of which, muscovite, phlogopite, vermiculite, lepidolite, and biotite, are widely used in industry. Lepidolite and zinnwaldite (lithium micas) and roscoelite (vanadium mica) are sources of lithium and vanadium. Muscovite, "white mica," is potassium mica. Theoretical formulas H2KAl3(SiO4)3. There are two varieties, distinguished as to color, known in industry as ruby and green. In crystals or "books," the colors each range through varying shades of red and green. However, when split into thin films, all micas, except biotite and phlogopite, are colorless and transparent. Muscovite frequently is stained red or black by thin films of iron oxide between the laminae. The staining usually is derived from magnetite, which sometimes is found as unaltered crystals.

Jan 1, 1949

By S. W. Parr

STUDIES relating to the behavior of coal toward oxygen may have for their purpose the determination of the fundamental factors that underlie spontaneous combustion, weathering and deterioration, and the general topic of storage, as well as those properties that have to do with the underlying principles of carbonization. There is also involved the possibility of developing information relating to the constitution of coal, or at least the chemical properties inherent in the type substances of which the coal is composed. It is the purpose here to record certain FIG. 1. results bearing on this latter idea of the chemical properties that characterize the main constituents of bituminous coal. The avidity of freshly mined coal for oxygen has long been known. What happens to the coal or to the oxygen is not so clear. Is the oxygen absorbed or chemically combined, and what are the conditions as to time, temperature, texture, or components that are most involved in the phenomenon?

Jan 6, 1925

By Jonathan Ludlow, Paul J. Guay

Based on two studies that were funded by the U.S. Department of Energy, the authors provide an overview of the benefits expected from mining deeper webs on United States longwalls. The first study, completed in November 1979, identified the limits and potential gains from taking deeper webs with presently available equipment. The second on-going study discusses the conceptual design and benefits of a future system for taking very deep webs.

Jan 1, 1981

By James A. Barr

PUMICE and pumice are varieties of volcanic ejecta formed from lavas of the more silicic types. Chemical analyses of pumice, pumicite and perlite, from which synthetic pumice is now produced, will generally fall within the limits 65 to 75 pct silica, 9 to 20 pct alumina, less than 8 pct combined alkalies (sodium and potassium oxides), less than 3 pct calcium and magnesium oxide, less than 3 pct iron oxide, with smaller amounts of manganese, titanium, phosphorus and other oxides. Perlite is characterized chemically by having, in addition to the percentages of oxides given above, as high as 6 pct combined water. PROPERTIES Pumice is a natural silicic foam glass produced by volcanic eruptions. The molten glass foam, upon rapid cooling, trapped the steam and volcanic gases that caused it to remain extremely porous and vesicular in structure. Pumice is found in the form of large lumps several cubic feet in volume and also in grains only a few millimeters in diameter. Chemically, pumicite is of the same range of composition as pumice. The distinction between pumice and pumicite is one of particle size; the coarser materials are pumice; the fine particles, an appreciable percentage of which is in the range of 100 to 325-mesh or finer, are pumicite. If the erupting volcano ejects a silicic lava containing much gas and water vapor, the sudden release of pressure tends to free the gas. The viscosity of the lava, its rate of cooling and the amount of gas evolved, all have part in determining the degree of expansion of the glassy particles and the fineness of the vesicle. If the lava is of the correct viscosity and there is not too much gas, a pumice may be formed. Large amounts of gas may cause complete disruption into pumicite.30 In 1916, Barbour gave the name "pumicite" to the volcanic ash of Nebraska and since then the name has been widely used in industrial circles for the finer-grained commercial varieties. The glass of pumice and pumicite is transparent and colorless. It

Jan 1, 1949

By G. Ansel, J. P. Doan

THE important literature concerning zirconium in magnesium-base alloys is predominantly contained in patent references. Sauerwald, Eisenreich, and Holub1-4 discovered the profound grain-refining influence of small amounts of zirconium on cast magnesium and the attendant increases in strength, and ductility. They extended their work to reveal that limited amounts of certain other elements, including zinc, could be added for further improvement in strength and hardness. British. Patent 5111376 relates to the parent discoveries of Sauerwald, Eisen¬reich, and Holub. All of these references deal primarily with casting characteristics and properties in the cast state. Minor mention is made of desirable tensile strength, ductility, and toughness of wrought Mg-Zr alloys* modified by one or more additional elements. No extensive reference in the literature" has been found to the particular characteristics of wrought Mg-Zn-Zr alloys, with which the present paper is concerned. - The work to be discussed represents essentially an extrusion study of the Mg-Zn-Zr alloys and indicates that this system is highly interesting in the wrought state both academically and commercially. Accordingly, an important aim of this paper is to describe the hot-workability, tension and compression properties, metal¬lography, and toughness of these alloys. Compositional variations are limited to the ranges o to 7 per cent Zn and o to I per cent Zr. EXPERIMENTAL PROCEDURE Alloying and Casting Alloying ingredients were cell mag¬nesium, commercial zinc (intermediate grade), and a chloride salt containing approximately 50 per cent ZrCl2 and 50 per cent alkali chlorides. This salt is produced by Titanium Alloy Manu¬facturing Company. Melting, alloying, and pouring procedure essentially followed the crucible process as described by Nelson.6 The magnesium was melted using Dow No. 310 flux, and the temperature raised to 1350° to 1400°F for the alloying operations. After alloying of the zinc, the zirconium containing salt was added in small portions with vigorous stirring. This is an adaptation of the method described in British Patent 533264.7 The alloying efficiency of zir¬conium was approximately 30 per cent. During the alloying of zirconium, fluorspar was added in amount required as a flux¬inspissating agent. Next the melt was refined with Dow No. 310 flux and held quietly for 15 min. Finally billets were cast in a book-type permanent mold

Jan 1, 1946

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By L. R. Page, J. J. Norton

EFFECTIVE methods for determining grade and reserves of pegmatites in advance of mining have been developed in recent years. When intensive work began on the economic geology of pegmatites during the early years of World War 11, it was widely believed that grade and reserves could be estimated only in a most general way. The literature indicated that not all pegmatite deposits are unpredictable, but statements emphasizing unpredictability and irregularity seem to have been more widely accepted. Many standard references reflect the prevailing opinion that minerals: are unsystematic in their occurrence in pegmatites. Pegmatites have been described as "notorious for their irregular structure," and minerals within pegmatites as "irregularly distributed." "irregularly disseminated," of "erratic occurrence," "proverbially erratic in distribution," "characterized by extreme irregularity in ... size and distribution of the essential minerals, and variety and proportion of the accessory minerals," and "spotty.'"" Over many years, however, geologic techniques have been applied with increasing success to economic analysis of pegmatites. Investigations, chiefly since 1939, have shown that mineral distribution and structure of pegmatites are largely systematic and that detailed geologic study can be used to predict the size and shape of mineral deposits in pegmatites. Because the writers are most familiar with the pegmatites of the Black Hills, S. D., examples cited are from that area." Pegmatites mined in other dis- * All examples are described more cornpletely elsewhere.: tricts are similar to those in the Black Hills," and the techniques described here have been applied by geologists and engineers working in other districts. In actual practice few pegmatite mine operators attempt to make accurate estimates of grade and reserves in advance of mining. Many deposits are too small for mining except on a very small scale; few pegmatite mines have more than ten employes. Hence there is little systematic preparation for mining, and the capital outlay may be so small that only a general knowledge of reserves is necessary. Technical personnel are rarely employed by pegmatite mine operators to make such estimates. In the future, however, as capital outlay becomes larger, estimates of grade and reserves will have to be more accurate. Geologic Aspects of Determining Grade and Reserves Estimating grade and reserves requires that the type of pegmatite, the size and shape, and the internal structure be determined by detailed geologic mapping and careful mineralogic study. The wide variations in the texture and distribution of minerals within many pegmatite deposits make a thorough geologic study of this kind necessary before it is possible to decide what sampling methods should be used to determine mineral content or grade. Types of Pegmatites: The first step in economic appraisal of a pegmatite is to determine the min-eralogical and structural type. In general, pegmatites may be classified into two groups: 1) those in which component minerals are more or less evenly distributed throughout the entire body and show relatively minor variations in texture, and 2) those in which component minerals have been segregated into units with recognizable differences in texture, mineralogy. or both. Johnston" has classified these types of pegmatites as homogeneous and heterogeneous, respectively. Cameron et al.10 have used the terms ~inzoned and zoned for similar types. The difference between the homogeneous and heterogeneous types is of great commercial importance. Homogeneous pegmatites can seldom be mined where the products are concentrated by the hand methods now commonly used, but they have been mined in a few places where a milling process has

Jan 1, 1957

By Paul A. Flinn, Jean-Marie Robert Genin

The MCssbauer effect was used to study the distribution of carbon in Fe-C alloys of high carbon content during room-temperature aging. In freshly formed rnartensite the carbon distribution is approximately random; carbon clustering occurs dun'ng aging. In the retained austete the carbon atoms are isolated, suggesting an efiective repulsion; and no rearrangement during room-temperature aging is evident. The kinetics of the carbon clustering in martensite has been studied in detail at 0" . 10". and 20°C. The time and temperature dependence observed is sinzilar to that reported for a variety of other aging effects, such as resistance change, hardness increase, and recovery of internal friction. The stabilization of the martensite kransformation also appears to be related to the clustering effect. DESPITE extensive efforts since the early days of Reaumur, the mechanism which provides the strengthening of steel remains controversial in many cases for several reasons: 1) The structure of as-quenched martensite is not well-determined. 2) Experimental methods capable of distinguishing between various hardening mechanisms are not well-developed. 3) The temperature of formation of many low-alloy martensites is so high that the martensite formed during quenching may be already tempered to some extent before any observation. Among all the hardening phenomena, the most puzzling one occurs at room temperature, where no structural changes have been detected by the usual methods of X-ray diffraction or electron microscopy. However, a new and more sensitive technique became available with the discovery of the MBssbauer effect. This effect makes possible the detection of changes in the local environment of iron atoms in solid solution. It has been extensively used in the study of substitutional alloy systems, for example, Fe-Al,1 Fe-Si,2,3 Fe-Rh,4 and Fe-Ni.5 Making use of the possibility of obtaining new structural information, we undertook an investigation of the aging of high-carbon Fe-C martensite to follow the structural changes involved in the aging at room temperature. Preliminary results6 showed that a clustering of the carbon atoms occurs with time. A systematic study of the kinetics of the process showed a striking similarity to the kinetics of stabilization of the marten-sitic transformation, thus suggesting further investigation of the relationship. EXPERIMENTAL TECHNIQUE To eliminate difficulties with the aging of martensite prior to the first experimental measurements, we needed an alloy with an M, temperature not above room temperature. Other investigators7 were misled by results obtained on alloys which transformed above room temperature and underwent structural changes prior to the first Mossbauer measurements. Winchell and cohen8 dealt with this difficulty by using a third element, nickel, to depress the MS below room temperature. The presence of nickel did not seriously interfere with hardness or resistivity measurements, but it would complicate the interpretation of the Mossbauer data by increasing the variety of iron environments. We chose, therefore, to obtain the necessary lowering of the M, simply by increasing the carbon content. After the first quench to room temperature, our specimens are retained austenite, which we later quench into liquid nitrogen. The martensitic transformation takes place suddenly, so that the as-quenched condition of the samples is retained, since the temperature is low enough to prevent any carbon diffusion. A Massbauer spectrum at 77°K can be taken and analyzed; after an appropriate up-quenching to the aging temperature, a new Mossbauer measurement at 77°K can be made. Fig. 1 shows a typical cycle of experiments. The samples were foils 25 p thick of high-purity

Jan 1, 1969

By Pradeep K. Rohatgi, David N. French, Surendar M. Jain, Clyde M. Adams

The effect of solute concentration and diffussivity on dendritic solidification of dilute binary aqueous solutions has been investigated; chlorides of sodium, potassium, lithiurn, and hydrogen were used as solutes. Dendrite spacings were measured in spherical droplets and in unidirectionally solidified specimens. In the droplets, the freezing rate is uniform over the entire specimen and remains constant from the beginning to the end of solidification. In the unidirec-tionally frozen specimens the freezing rate varies within a given volume of liquid during the solidification cycle; in addition, it varies with location uithin the specimen. Mass transport analysis has been used to calculate the supersaturation, AC, supercooling, AT, and transcerse growth velocity, V , of ice dendrites during solidijication from the dendrite spacings measured in the droplels. The ice dendrite spacing in a given solute increases lineary with the solule concentralion at a fixed freezing rate. The ualues of AC, AT, and V increase with an increase in solule concentration. The value of AT in the aqueous solution is of the same order of magnitude as in Al-Cu alloys of the same concentration; the dendrite spacings in Al-Cu alloys also increase with an increase in solute concentralion. For the jamily of aqueozrs solulions incestigaled, the dendrite spacing increases linearly with solute diffusivity at fixed values of concertralion and freezing ,rate. The values of ?C and ?T decrease, whereas the value of V increases with an increase in solule diffusicity. The measured dendrite spacings , L, can be expressed by the relatiun: L = K;(dfa/db) 4 K2C +K3D - K4 where dfs/d? is-change in fraction solid with time (freezing rate), C is solute concentration, D is solute diffusivit K1 = (14 * 4)pmin1'2, K2 = (70 ± 10) pl (moles)- K3 = (24 r 3) . l05 psec (cm)-~. K. = -132 ± 10) 1. FREEZING of solutions is almost always an ehunmix-ing" process because the composition of crystallizing solid generally differs from that of the parent liquid. " Solute concentration and transport are therefore in]portant considerations in solidification of solutions. The influence of these factors on the dendritic solutions produced from metallic solutions is of practical significance since the properties of the solid aggre-gate are often strongly influenced by dendrite spacing.''' Alexander and Fthines3 found that dendrite spac- ings generally increase with solute concentration in several metallic systems. Michael and Bever1 have observed an increase in a aluminum dendrite spacings in dilute A1-Cu alloys. Rohatgi and AdamsJ have reported a linear increase in a aluminum dendrite spacings with increasing copper contents up to 28 pct in A1-Cu alloys. Bolling and Tiller"' have theoretically examined the effects of solute concentration and diffusivity on the growth of cells and dendrites. Their analysis of dendritic growth assumes a steady-state growth and the maximum possible velocity for dendrite propagation. In addition, the quantitative analysis is restricted to dendrites of rotational symmetry and is therefore not directly applicable to the plate-shaped dendrites of ice obtained in the present study. There are practically no experimental observations of the effect of solute diffusivity on dendrite spacings in metallic systems. The reason appears to be the lack of experimental data on solute diffusion coefficients in liquid metallic solutions. The present work is concerned with the effect of solute concentration and diffusivity on dendritic solidification of dilute aqueous solutions: the solutes examined are potassium chloride. sodium chloride, lithium chloride. and hydrogen chloride. There were several reasons for selecting these solutes. The variation of dendrite spacing with freezing rate in these solutiolls is similar to that observed in A1-Cu alloys.8 These aqueous solutions have almost identical phase diagrams at dilute concentrations. Fig. 1. and the diffusion coefficients show very little variation with solute Concentration.9,10 Dendrite spacings were measured as a function of freezing rate. solute concentration. and solute diffusivity. Dendrite spacings were measured in two different types of freezing systems. droplet and unidirectional, respectively. In the droplet freezing system

Jan 1, 1970

By K. C. Li

ARSENIC and antimony are always grouped together by chemists, since they are both members of group V of the periodic table of elements and exhibit a general similarity in the formation of compounds. Metallurgists generally think of them as less closely related because they do not have similar uses. In metallurgical operations, especially lead and copper smelting, arsenic tends to go off as a vapor phase and collect as fume in the flues, while antimony tends to remain with the bullion. Broadly speaking, the frequency of occurrence, practical utility and the effects on associated metals of arsenic and antimony are such that the metallurgist is inclined to think of arsenic as a troublesome impurity in ores, but of antimony as a valuable constituent that is recovered either as a byproduct or through the metallurgical treatment of antimony ores. Estimating the world production of arsenic as about 40,000 tons annually, probably not more than about 200 tons yearly is produced and used in metallic form, whereas one half of the approximately 40,000 tons of antimony produced annually is metallic. ARSENIC The modern uses of arsenic differ little from ancient ones. Though it has been known from early times, its poisonous quality is almost the only one that yet finds extensive use. The shift in the past century from its utilization in poisoning people to the poisoning of insects, beginning in 1860, has not only led to a considerable increase in

Jan 1, 1953

By E. A. Smith, E. R. Parker

METALLURGISTS and engineers have always been interested in the mechanism of high-speed deformation because metals are rapidly deformed in various applications and manufacturing processes. The deformation of metals by impact loads has recently engaged the attention of a number of investigators. Many of their results have not been disclosed but some of the published investigations1-8 have shown that the tensile strength, yield strength and elongation generally increase with increasing strain rate. The investigation reported herein is an attempt to determine the reason for this increase in strength and elongation. Single-crystal copper specimens were broken in tension at impact velocities up to 100 ft. per sec. The distribution of slip bands in the fractured crystals was found to depend upon the strain rate. In the bars broken at high speeds, the slip bands appear to be more numerous. This might account for the higher strength as well as the greater elongation. EXPERIMENTAL PROCEDURE Single crystals of copper (approximately 99.98 per cent) were made in graphite molds by the conventional method of lowering the mold out of the hot zone of a hydrogen furnace at a rate of one inch per hour. Solidification progressed from the bottom upward, forming a single crystal. The crystals were about 0.30 in. in diameter and 4 in. long. They were made into test bars by sliding threaded steel bushings over each end of a crystal and then flowing silver solder between the crystal and the bushing. The inside diameter of the bushings was slightly greater than the diameter of the crystals, to allow space for the silver solder. The bushings were placed so that the gauge length of the crystals was one inch. The assembly is shown in Fig. I, with two views of a fractured crystal. Annealed polycrystalline copper bars of similar shape were machined from solid stock. X-ray measurements were made on all single crystals to determine their orienta¬tions. The results are shown in Fig. 2, where the location of the axis of each specimen is indicated on a standard projection. The bars were broken in a commercial variable-velocity tension im¬pact machine, which has been described in detail elsewhere.7,8 The stress and strain were recorded by means of wire strain gauges and a special commercial oscillo-raph, also described in detail elsewhere.9,10 The equipment and method can be briefly described as follows. The impact machine consists of a motor-driven flywheel containing a two-pronged hammer. This hammer is held retracted in the flywheel

Jan 1, 1944

By Harold B. Goldman, Don Reining

The sand and gravel industry is the largest nonfuel mineral industry in the nation (Drake, 1972), Table 1. In 1970, the production of sand and gravel totaled 944 million tons valued at $1.1 billion. California, which leads the nation with more than 140 million tons, together with Michigan, Ohio, Minnesota, Illinois, Wisconsin, and New York, account for 43 % of the total production in the nation. In commercial usage, "sand" applies to rock or mineral fragments ranging in size from particles retained on a No. 200 sieve (0.074 mm openings) to those passing a No, 4 sieve (4.76 mm openings). "Gravel" consists of rock or mineral fragments larger than 4.76 mm, ranging up to 3%-in. maximum size. The construction industry consumes 96% of the sand and gravel produced; the remainder is sand used for specialized products such as glass (see the chapter on "Silica and Silicon"). Utilization The building industry uses sand and gravel chiefly as aggregate in portland cement concrete, mortar, and plaster; the paving industry uses sand and gravel in both asphaltic mixtures and portland cement concrete. Aggregate is commonly designated as the inert fragmental material which is bound into a conglomerate mass by a cementing material such as portland cement, asphalt, or gypsum plaster.

Jan 1, 1975

By Arthur F. Daily

8.5-1. Bucket Line Dredge. INTRODUCTION. The modern bucket-line dredge for mining placer deposits is a combined floating excavating machine and a gravity concentration system. Material is excavated at the forward end by the buckets, elevated, washed and screened, concentrated for recovery of valuable mineral, and discharged off the stern as coarse and small fractions. The end product is a concentrate consisting either of the valuable mineral(s) and associated heavy minerals, which are taken to a treatment plant on shore; or in the case of gold, a clean amalgam ready for retorting. The bucket-line dredge may be adapted for purposes other than mining for valuable mineral by installing, in lieu of a concentrating system, machinery for pumping all of the solids ashore in a pulp, or for producing washed gravel in selected size fractions of which all or a selected fraction is pumped to disposal areas on shore or into side barges. The two principal types of bucket-line dredges designed for mining are: 1) those having an inclined belt conveyor stacker to discharge the coarse fraction of washed tailing well astern of the hull, and sluices to discharge the sand fraction (Fig. 8.5-1), and 2) those having only sluices for discharge of all tailing astern. Use of the latter type has been confined, with few exceptions, to mining cassiterite-bearing deposits in Malaysia and at sea off Indonesia. Small dredges having only flumes for washing and concentrating all material dug by the buckets have been used for mining shallow stream valley deposits. GENERAL ARRANGEMENT. The general arrangement of a modern bucket-line dredge for mining tin, with a primary concentrating plant on board, is shown in Fig. 8.5-2. The hull and superstructure of most dredges are fabricated of structural steel; wood also has been used for both small and large dredges with complete satisfaction. All-riveted or partially welded unit hulls have been widely used and are desirable for exceptionally severe service. The hull

Jan 1, 1968